US4196117A - Alkylated 1,1'-biphenyl-2,2'-diyl phosphites and stabilized compositions - Google Patents

Alkylated 1,1'-biphenyl-2,2'-diyl phosphites and stabilized compositions Download PDF

Info

Publication number
US4196117A
US4196117A US05/866,748 US86674878A US4196117A US 4196117 A US4196117 A US 4196117A US 86674878 A US86674878 A US 86674878A US 4196117 A US4196117 A US 4196117A
Authority
US
United States
Prior art keywords
tert
butyl
compound
diyl
phosphite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/866,748
Inventor
John d. Spivack
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
Ciba Geigy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Corp filed Critical Ciba Geigy Corp
Priority to US05/866,748 priority Critical patent/US4196117A/en
Priority to DE7878101825T priority patent/DE2861920D1/en
Priority to EP78101825A priority patent/EP0002821B1/en
Priority to CA318,804A priority patent/CA1104580A/en
Priority to JP16457378A priority patent/JPS54100391A/en
Priority to US06/093,786 priority patent/US4288391A/en
Application granted granted Critical
Publication of US4196117A publication Critical patent/US4196117A/en
Priority to US06/246,341 priority patent/US4351759A/en
Assigned to CIBA SPECIALTY CHEMICALS CORPORATION reassignment CIBA SPECIALTY CHEMICALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CIBA-GEIGY CORPORATION
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5398—Phosphorus bound to sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657109—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
    • C07F9/657127—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s) condensed with carbocyclic or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657109—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s)
    • C07F9/657136—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms esters of oxyacids of phosphorus in which one or more exocyclic oxygen atoms have been replaced by (a) sulfur atom(s) the molecule containing more than one cyclic phosphorus atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/925—Natural rubber compositions having nonreactive materials, i.e. NRM, other than: carbon, silicon dioxide, glass titanium dioxide, water, hydrocarbon or halohydrocarbon
    • Y10S524/929—Natural rubber broadly disclosed, nonclaimed

Definitions

  • Organic polymeric materials such as plastics and resins and lubricating and mineral oil are subject to thermal, oxidative and photodegradation.
  • stabilizers are known in the art for stabilizing various substrates. Their effectiveness varies depending on the causes of degradation and the substrate stabilized. During the course of this work it was discovered that stabilizers that are very effective long term antioxidants are relatively poor process stabilizers which require stabilization of the substrate, against thermal degradation for a short time but at a relatively high temperature. Many stabilizers are relatively incompatible with the substrates which causes problems during the life of a product and lessens the stabilizer's effectiveness. Some stabilizers are either too volatile or thermally or hydrolytically unstable to be practical as commercial stabilizers.
  • the phosphites of this invention possess an unusual combination of desirable properties as compared to the prior art phosphites which makes these compounds particularly effective and useful as stabilizers.
  • the prior art discloses unhindered 2,2'-biphenylenephenylphosphite and 2,2'-methylene bis-(dialkylphenyl)phenylphosphites (Chem. Abst. 68, 12597Q (1968), Chem. Abst. 73, 15657 A (1970), Chem. Abst. 75, 130242Q (1971) and Soviet Union Pat. Nos. 378,389 and 429,070). These compounds are said to be stabilizers of various polymers. However the phosphites of this invention are much more effective especially as process stabilizers for polyolefins and other substrates, both in preventing polymer chain scission as well as discoloration during high temperature processing.
  • This invention is directed to alkylated 1,1'-biphenyl-2,2'-diyl phosphites and to polymeric and non-polymeric organic materials stabilized with said phosphites. More specifically the phosphites of this invention can be represented by the formula ##STR1## wherein R is an alkyl group of 1 to 18 carbon atoms,
  • R 1 is hydrogen or an alkyl group of 1 to 18 carbon atoms
  • R 2 is an alkyl group of 1 to 18 carbon atoms, phenyl, phenyl substituted with up to 3 alkyl groups each having 1 to 8 carbon atoms, or a group of the formula ##STR2## where R 3 is a divalent hydrocarbyl group selected from alkylene, arylene or allylene, and X is oxygen or sulfur.
  • the R groups are preferably straight-chain or branched alkyl with 1-8 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, tert.-butyl, 2-ethylhexyl and n-octyl and tert-octyl.
  • ⁇ -branched alkyl radicals with 3-8 carbon atoms are more preferred.
  • the groups tert-butyl and tert-octyl are especially preferred. Also especially preferred is for the R 1 group to be in the para position to oxygen, particularly if R 1 is tert.-alkyl.
  • R 1 can be hydrogen or alkyl of 1 to 18 carbons, preferably it is an alkyl group of 1 to 8 carbon atoms, either straight-chain or branched-chain. Especially preferred is tert.-alkyl of 4 to 8 carbon atoms.
  • the group R 2 can be alkyl of 1 to 18 carbon atoms, such as methyl, ethyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl, octadecyl and the like; or it can be phenyl or alkyl substituted phenyl, such as tolyl, xylyl, mesitylyl, ethylphenyl, butyl-phenyl, 3,5-dibutylphenyl, p-octyl-phenyl, 3,5-dioctylphenyl and the like.
  • R 2 is a phenyl group having at least one brached alkyl group.
  • R 2 is 2-tert-butylphenyl, 2,4-di-tert-butyl-phenyl, 2,4,6-tri-tert-butylphenyl, 2-tert-butyl-5-methylphenyl, 2,6-di-tert-butyl-phenyl and 2,6-di-tert-butyl-4-methyl-phenyl, 2,4-di-tert-octylphenyl.
  • the R 3 group can be straight or branched chain alkylene of 1 to 12 carbon atoms or arylene of 6 to 30 carbon atoms.
  • alkylene it is preferably 2 to 6 carbon atoms, such as ethylene, propylene, trimethylene, butylene, tetramethylene, pentylene, hexamethylene, hexylene and the like.
  • arylene it can be unsubstituted or substituted with 1 to 4 alkyl groups each alkyl having 1 to 8 and preferably 1 to 4 carbon atoms.
  • Illustrative examples of arylene groups are phenylene, tolylene, 1,3,5-tri-methylphenylene, 1,2,4,5-tetramethylphenylene; 2,5-di-tert-butylphenylene, or the like.
  • Arylene can also be a polynuclear arylene such as biphenylene or alkylenediphenylene where the alkylene has from 1 to 25 carbons, as for example, methylenediphenylene, isopropylenediphenylene and pentacosylenediphenylene.
  • R 3 is an alkylene of 2 to 6 carbons, phenylene or a phenyl substituted with one or two alkyl groups, each having 1 to 4 carbons.
  • the alkylated 1,1'-biphenyl-2,2'-diyl phosphites of this invention can be prepared by reacting an alkylated 2,2'-biphenol with phosphorus trichloride in a solvent to give the corresponding phosphorochloridite which in turn is reacted with an alkali metal alcoholate or phenolate to yield the desired product.
  • the solvent is preferably aromatic, such as benzene, toluene, xylene and the like.
  • a reaction temperature from room temperature to the reflux temperature of the reaction medium.
  • Another method for preparing the compounds of this invention involves reacting the phosphorochlordite with an appropriate alcohol or phenol optionally in the presence of a protan acceptor such as a tertiary amine, for example, triethylamine or pyridine.
  • a protan acceptor such as a tertiary amine, for example, triethylamine or pyridine.
  • the compounds of this invention are effective light stabilizers and/or antioxidants in a wide range of organic polymers.
  • Polymers which can be stabilized include:
  • Polymers which are derived from mono- or diolefins e.g., polyethylene which can optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polyisoprene, polybutadiene.
  • Copolymers of the monomers based on the homopolymers cited under (1) for example ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers as well as terpolymers of ethylene and propylene with a diene, for example hexadiene, dicyclopentadiene or ethylidene norbornene, and copolymers of ⁇ -olefins, e.g., ethylene, with acrylic or methacrylic acid.
  • ethylene/propylene copolymers for example ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers as well as terpolymers of ethylene and propylene with a diene, for example hexadiene, dicyclopenta
  • Copolymers of styrene and of ⁇ -methylstyrene for example styrene/butadiene copolymers, styrene/acrylonitrile copolymers, styrene/acrylonitrile/methylacrylate copolymers, styrene/acrylonitrile/acrylic ester copolymers, styrene/acrylonitrile copolymers modified with acrylic ester polymers to provide impact strength as well as block copolymers, e.g., styrene/butadiene/styrene block copolymers.
  • Graft copolymers of styrene for example the graft polymer of styrene to polybutadiene, the graft polymer of styrene with acrylonitrile to polybutadiene as well as mixtures thereof with the copolymers cited under (5), commonly referred to as acrylonitrile/butadiene/styrene or ABS plastics.
  • Halogen-containing vinyl polymers for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubbers, vinyl chloride/vinylidene chloride copolymers, vinyl chloride/vinyl acetate copolymers, vinylidene chloride/vinyl acetate copolymers.
  • Polymers which are derived from unsaturated alcohols and amines and from the acyl derivatives thereof or acetals for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and copolymers thereof with other vinyl compounds, for example ethylene/vinyl acetate copolymers.
  • Homopolymers and copolymers which are derived from epoxides for example polyethylene oxide or the polymers which are derived from bis-glycidyl ethers.
  • Polyacetals for example polyoxymethylene, as well as polyoxymethylenes which contain ethylene oxide as comonomer.
  • Polyalkylene oxides for example polyoxyethylene, polypropylene oxide or polyisobutylene oxide.
  • Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-m-phenylene-isophthalamide.
  • Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene glycol terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate.
  • Cross-linked polymers which are derived from aldehydes on the one hand and from phenols, ureas and melamines on the other, for example phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins.
  • Alkyd resins for example glycerol/phthalic acid resins and mixtures thereof with melamine/formaldehyde resins.
  • Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols as well as from vinyl compounds as cross-linking agents and also the halogen-containing, flame-resistant modifications thereof.
  • Natural polymers for example cellulose, rubber, as well as the chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates and the cellulose ethers, for example methyl cellulose.
  • Compounds of this invention are particularly effective in stabilizing organic materials such as plastics, polymers, resins in addition to mineral and synthetic fluids such as lubricating oils, circulating oils, etc.
  • the compounds of this invention are particularly useful as stabilizers, especially for the protection of polyolefins, for instance, polyethylene, polypropylene, polyisobutylene, poly(butene-1), poly(pentene-1), poly(3-methylbutene-1), poly(4-methylpentene-1), various ethylene-propylene copolymers and the like.
  • polyolefins for instance, polyethylene, polypropylene, polyisobutylene, poly(butene-1), poly(pentene-1), poly(3-methylbutene-1), poly(4-methylpentene-1), various ethylene-propylene copolymers and the like.
  • polystyrene including impact polystyrene, ABS resin, SBR, isoprene, as well as natural rubber, polyesters including polyethylene terephthalate and polybutylene terephthalate, including copolymers.
  • polyurethanes polycarbonates, polyamides such as nylon 6, 6/6 and the like as well as copolyamides and polysulfones.
  • the compounds of this invention may be used alone as the sole stabilizer having either mainly an antioxidant function or a light stabilizing function or the stabilizer may combine utility as an antioxidant and light stabilizer.
  • the stabilizers may be used with phenolic antioxidants, lubricants such as calcium stearate, pigments, colorants or dyes, UV absorbers, light stabilizers such as hindered amines, metal deactivators, talc and other fillers, etc.
  • the stabilizers of this invention are employed from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application.
  • An advantageous range is from about 0.05 to about 2%, and especially 0.1 to about 1%.
  • Compounds of this invention stabilize polymers especially during high temperature processing with relatively little change in color, even though the polymer may undergo a number of extrusions.
  • polymers in which this property is especially apparent are polypropylene, polyethylene, styrenics such as ABS, polyethylene- and polybutylene-terephthalates, polycarbonates, natural rubber, synthetic rubber such as SBR.
  • process stabilizers While many compounds which have been used as process stabilizers are sufficiently effective as process stabilizers for polyolefins only in the presence of costabilizers such as phenolic antioxidants, compounds of this invention are effective in the absence of phenolic antioxidants. Many of the compounds of this invention combine process stabilizing properties with the ability to confer light stability on the polymer.
  • a particularly important property for stabilizers which are trivalent phosphorus esters is their non-hygroscopicity and resistance to hydrolysis in the presence of moisture in the atmosphere during ambient storage. Hygroscopicity frequently results in difficulty in incorporating the process stabilizer uniformly into the polymer causing stickiness and blockage during compounding, while hydrolysis of the phosphorus ester stabilizers during storage frequently results in compounds which are less effective.
  • the stabilizers of formula I may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
  • the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
  • the stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following:
  • Simple 2.6-dialkylphenols such as, for example, 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.
  • alkylated hydroquinones such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.
  • alkylated hydroquinones such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-di-ter
  • Hydroxylated thiodiphenyl ethers such as, for example, 2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulphide.
  • 2,2'-thio-bis-(6-tert.-butyl-4-methylphenol 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4
  • Alkylidene-bisphenols such as, for example, 2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol), 4,4'-methylene-bis-(6-tert.-butyl-2-methylphenol), 4,4'-methylene-bis-(2,6-di-tert.-butylphenol), 2,6-di-(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-( ⁇ -methylcyclohexyl)-phenol], 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)-butane, 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)
  • O-, N- and S-benzyl compounds such as, for example, 3,5,3',5'-tetra-tert.-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.
  • 3,5,3',5'-tetra-tert.-butyl-4,4'-dihydroxydibenzyl ether octadecyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate
  • tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine bis-(4-tert.-butyl-3-hydroxy-2,6-di
  • Hydroxybenzylated malonates such as, for example, dioctadecyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)-malonate, dioctadecyl 2-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercapto-ethyl 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate and di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate.
  • dioctadecyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)-malonate dioctadecyl 2-(3-tert.-butyl-4-hydroxy-5-
  • Hydroxybenzyl-aromatic compounds such as, for example, 1,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-di-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-phenol.
  • 1.8 s-Triazine compounds such as, for example, 2,4-bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyanilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-s-triazine and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl) iso
  • esters of ⁇ -(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2,2,2]octane.
  • monohydric or polyhydric alcohols such as, for example, with methanol
  • esters of ⁇ -(5-tert.-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
  • esters of 3,5-di-tert.-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiglycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]-octane, especially the tetra-bis ester of pentaerythritol.
  • Benzylphosphonates such as, for example, dimethyl 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, diethyl 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, dioctadecyl 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate and dioctadecyl 5-tert.-butyl-4-hydroxy-3-methylbenzyl-phosphonate.
  • Aminoaryl derivatives e.g. phenyl-1-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and dioctyliminodibenzyl, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline.
  • Octylated diphenylamine nonylated diphenylamine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sect.octyl-p-phenylenediamine, N-phenyl-N'-sec.-octyl-p-phenylenediamine, N,N'-di-(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-dimethyl-N,N'-di-(sec.-octyl)-p-phenylenediamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.-butylaniline, diphenylamineacetone condensation product, aldol-1-naphthylamine and
  • 2-Hydroxybenzophenones e.g. the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy-derivative.
  • 1,3-bis-(2'-Hydroxybenzoyl)-benzenes e.g. 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene or 1,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.
  • Esters of optionally substituted benzoic acids e.g. phenylsalicylate, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoylresorcin, 3,5-di-tert.-butyl-4-hydroxybenzoic acid-2,4-di-tert.-butylphenyl ester or -octadecyl ester or -2-methyl-4,6-di-tert.-butyl ester.
  • benzoic acids e.g. phenylsalicylate, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoylresorcin, 3,5-di-tert.-butyl-4-hydroxybenzoic
  • Sterically hindered amines e.g. 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-tetramethylpiperidyl)-sebacate or 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]decane-2,4-dione.
  • Oxalic acid diamides e.g. 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.-butyl-oxanolide, 2,2'-di-dodecyloxy-5,5'-di-tert.-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide and the mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert.-butyl-oxanilide, or mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilide, or
  • Metal deactivators e.g. oxanilide, isophthalic acid dihyrazide, sebacic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetal-adipic acid dihydrazide, N,N'-bis-salicyloyloxalic acid dihydrazide, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)hydrazine, N-salicyloyl-N'-salicylalhydrazine, 3-salicyloylamino-1,2,4-triazole or N,N'-bis-salicyloyl-thiopropionic acid dihydrazide.
  • oxanilide isophthalic acid dihyrazide
  • Basic co-stabilisers e.g. alkali metal salts and alkaline-earth metal salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-behenate, Na-ricinoleate or K-palmitate.
  • Nucleation agents e.g. 4-tert.-butylbenzoic acid, adipic acid or diphenylacetic acid.
  • Phosphites such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphospha[5,5]-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.
  • thiosynergists such as dilaurylthiodiproprionate or distearylthiodipropionate
  • lubricants such as stearyl alcohol fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, optical brighteners, flameproofing agents and antistatic agents.
  • the reaction mixture was clarified by filtration of the precipitated potassium chloride and the product isolated as a residue by distillation of the toluene at reduced pressures.
  • the product was isolated as crystals after crystallization from a solvent mixture of acetonitrile and toluene yielding white crystals melting at 195°-197°.
  • the compound of this example was made by substantially the same method as Example 2 by reacting (4,4'-6,6'-tetra-tert.-butyl-2,2'-biphenylene)phosphorochlorodite with potassium 2,6-di-tert.-butyl-4-methylphenolate. After crystallization, the product is obtained as white crystals melting at 152°-155° C.
  • the compound of this example was made by substantially the same method as Example 2 by reacting 3,3',5,5'-tetra-tert.butyl-1,1'-biphenyl-2,2'-diyl) phosphorochlorodite with potassium 2,4,6-tri-tert. phenolate. After crystallization, the product is obtained as white crystals melting at 210°-212°.
  • the compound of this Example was made by the same procedure as Examples by reacting two molar proportions of tetra-3,3'5,5'-tert.butyl -1,1'-biphenyl-2,2'-diyl phosphorochloridite (Example 1) with one molar proportion of 1,3-propanedithiol in the presence to triethylamine. After crystallization the product melted at 190°-193° C.
  • the compound of this example is made by the same procedure as Example 5 by reacting two molar proportions of the chloridite of Example IV with one molar proportion of 4,4'-methylene-bis (2,6-di-tert.-butylphenol) in the presence of triethylamine.
  • the compound of this example was made by substantially the same procedure as Example 5 by reacting equimolar quantities of the chloridite of Example 1 with n-octadecanol in the presence of triethylamine. After purification by chromatography and by crystallization the product was obtained as white crystals melting at 38°-41° C.
  • Stabilizers were solvent blended into polypropylene as solutions in methylene chloride and, after removal of the solvent by evaporation at reduced pressure, the resin was extruded using the following extruder conditions:
  • melt flow rate was determined by ASTM method 1238 condition L.
  • the melt flow rate varies directly as the transducer pressure and both are a measure of the molecular weight for a specific type of polymer.

Abstract

Alkylated 1,1'-biphenyl-2,2'-diyl phosphiates are prepared by reacting alkylated 2,2'-biphenol with phosphorus trichloride in an organic solvent an then reacting the intermediate with an alcohol or a thiol. Said phosphites are useful as stabilizers of organic polymers and lubricating oils, especially as process stabilzers for polyolefins, polyesters and polycarbonates.

Description

BACKGROUND OF THE INVENTION
Organic polymeric materials such as plastics and resins and lubricating and mineral oil are subject to thermal, oxidative and photodegradation. A great variety of stabilizers are known in the art for stabilizing various substrates. Their effectiveness varies depending on the causes of degradation and the substrate stabilized. During the course of this work it was discovered that stabilizers that are very effective long term antioxidants are relatively poor process stabilizers which require stabilization of the substrate, against thermal degradation for a short time but at a relatively high temperature. Many stabilizers are relatively incompatible with the substrates which causes problems during the life of a product and lessens the stabilizer's effectiveness. Some stabilizers are either too volatile or thermally or hydrolytically unstable to be practical as commercial stabilizers.
The phosphites of this invention possess an unusual combination of desirable properties as compared to the prior art phosphites which makes these compounds particularly effective and useful as stabilizers. The prior art discloses unhindered 2,2'-biphenylenephenylphosphite and 2,2'-methylene bis-(dialkylphenyl)phenylphosphites (Chem. Abst. 68, 12597Q (1968), Chem. Abst. 73, 15657 A (1970), Chem. Abst. 75, 130242Q (1971) and Soviet Union Pat. Nos. 378,389 and 429,070). These compounds are said to be stabilizers of various polymers. However the phosphites of this invention are much more effective especially as process stabilizers for polyolefins and other substrates, both in preventing polymer chain scission as well as discoloration during high temperature processing.
DETAILED DISCLOSURE
This invention is directed to alkylated 1,1'-biphenyl-2,2'-diyl phosphites and to polymeric and non-polymeric organic materials stabilized with said phosphites. More specifically the phosphites of this invention can be represented by the formula ##STR1## wherein R is an alkyl group of 1 to 18 carbon atoms,
R1 is hydrogen or an alkyl group of 1 to 18 carbon atoms and
R2 is an alkyl group of 1 to 18 carbon atoms, phenyl, phenyl substituted with up to 3 alkyl groups each having 1 to 8 carbon atoms, or a group of the formula ##STR2## where R3 is a divalent hydrocarbyl group selected from alkylene, arylene or allylene, and X is oxygen or sulfur.
The R groups are preferably straight-chain or branched alkyl with 1-8 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, tert.-butyl, 2-ethylhexyl and n-octyl and tert-octyl. α-branched alkyl radicals with 3-8 carbon atoms are more preferred. The groups tert-butyl and tert-octyl are especially preferred. Also especially preferred is for the R1 group to be in the para position to oxygen, particularly if R1 is tert.-alkyl.
Although R1 can be hydrogen or alkyl of 1 to 18 carbons, preferably it is an alkyl group of 1 to 8 carbon atoms, either straight-chain or branched-chain. Especially preferred is tert.-alkyl of 4 to 8 carbon atoms.
The group R2 can be alkyl of 1 to 18 carbon atoms, such as methyl, ethyl, butyl, hexyl, heptyl, octyl, decyl, dodecyl, octadecyl and the like; or it can be phenyl or alkyl substituted phenyl, such as tolyl, xylyl, mesitylyl, ethylphenyl, butyl-phenyl, 3,5-dibutylphenyl, p-octyl-phenyl, 3,5-dioctylphenyl and the like. Preferably R2 is a phenyl group having at least one brached alkyl group. Most preferably R2 is 2-tert-butylphenyl, 2,4-di-tert-butyl-phenyl, 2,4,6-tri-tert-butylphenyl, 2-tert-butyl-5-methylphenyl, 2,6-di-tert-butyl-phenyl and 2,6-di-tert-butyl-4-methyl-phenyl, 2,4-di-tert-octylphenyl.
The R3 group can be straight or branched chain alkylene of 1 to 12 carbon atoms or arylene of 6 to 30 carbon atoms.
Where it is alkylene it is preferably 2 to 6 carbon atoms, such as ethylene, propylene, trimethylene, butylene, tetramethylene, pentylene, hexamethylene, hexylene and the like. Where it is arylene it can be unsubstituted or substituted with 1 to 4 alkyl groups each alkyl having 1 to 8 and preferably 1 to 4 carbon atoms. Illustrative examples of arylene groups are phenylene, tolylene, 1,3,5-tri-methylphenylene, 1,2,4,5-tetramethylphenylene; 2,5-di-tert-butylphenylene, or the like. Arylene can also be a polynuclear arylene such as biphenylene or alkylenediphenylene where the alkylene has from 1 to 25 carbons, as for example, methylenediphenylene, isopropylenediphenylene and pentacosylenediphenylene. Most preferably R3 is an alkylene of 2 to 6 carbons, phenylene or a phenyl substituted with one or two alkyl groups, each having 1 to 4 carbons.
The alkylated 1,1'-biphenyl-2,2'-diyl phosphites of this invention can be prepared by reacting an alkylated 2,2'-biphenol with phosphorus trichloride in a solvent to give the corresponding phosphorochloridite which in turn is reacted with an alkali metal alcoholate or phenolate to yield the desired product. The solvent is preferably aromatic, such as benzene, toluene, xylene and the like. A reaction temperature from room temperature to the reflux temperature of the reaction medium. Another method for preparing the compounds of this invention involves reacting the phosphorochlordite with an appropriate alcohol or phenol optionally in the presence of a protan acceptor such as a tertiary amine, for example, triethylamine or pyridine.
The compounds of this invention are effective light stabilizers and/or antioxidants in a wide range of organic polymers. Polymers which can be stabilized include:
1. Polymers which are derived from mono- or diolefins, e.g., polyethylene which can optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, polyisoprene, polybutadiene.
2. Mixtures of the homopolymers cited under (1), for example mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, polypropylene and polyisobutylene.
3. Copolymers of the monomers based on the homopolymers cited under (1), for example ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers as well as terpolymers of ethylene and propylene with a diene, for example hexadiene, dicyclopentadiene or ethylidene norbornene, and copolymers of α-olefins, e.g., ethylene, with acrylic or methacrylic acid.
4. Polystyrene.
5. Copolymers of styrene and of α-methylstyrene, for example styrene/butadiene copolymers, styrene/acrylonitrile copolymers, styrene/acrylonitrile/methylacrylate copolymers, styrene/acrylonitrile/acrylic ester copolymers, styrene/acrylonitrile copolymers modified with acrylic ester polymers to provide impact strength as well as block copolymers, e.g., styrene/butadiene/styrene block copolymers.
6. Graft copolymers of styrene, for example the graft polymer of styrene to polybutadiene, the graft polymer of styrene with acrylonitrile to polybutadiene as well as mixtures thereof with the copolymers cited under (5), commonly referred to as acrylonitrile/butadiene/styrene or ABS plastics.
7. Halogen-containing vinyl polymers, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubbers, vinyl chloride/vinylidene chloride copolymers, vinyl chloride/vinyl acetate copolymers, vinylidene chloride/vinyl acetate copolymers.
8. Polymers which are derived from α,β-unsaturated acids and derivatives thereof, polyacrylates and polymethacrylates, polyacrylic amides and polyacrylonitrile.
9. Polymers which are derived from unsaturated alcohols and amines and from the acyl derivatives thereof or acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and copolymers thereof with other vinyl compounds, for example ethylene/vinyl acetate copolymers.
10. Homopolymers and copolymers which are derived from epoxides, for example polyethylene oxide or the polymers which are derived from bis-glycidyl ethers.
11. Polyacetals, for example polyoxymethylene, as well as polyoxymethylenes which contain ethylene oxide as comonomer.
12. Polyalkylene oxides, for example polyoxyethylene, polypropylene oxide or polyisobutylene oxide.
13. Polyphenylene oxides.
14. Polyurethanes and polyureas.
15. Polycarbonates.
16. Polysulphones.
17. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, poly-m-phenylene-isophthalamide.
18. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene glycol terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate.
19. Cross-linked polymers which are derived from aldehydes on the one hand and from phenols, ureas and melamines on the other, for example phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins.
20. Alkyd resins, for example glycerol/phthalic acid resins and mixtures thereof with melamine/formaldehyde resins.
21. Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols as well as from vinyl compounds as cross-linking agents and also the halogen-containing, flame-resistant modifications thereof.
22. Natural polymers, for example cellulose, rubber, as well as the chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates and the cellulose ethers, for example methyl cellulose.
Compounds of this invention are particularly effective in stabilizing organic materials such as plastics, polymers, resins in addition to mineral and synthetic fluids such as lubricating oils, circulating oils, etc.
The compounds of this invention are particularly useful as stabilizers, especially for the protection of polyolefins, for instance, polyethylene, polypropylene, polyisobutylene, poly(butene-1), poly(pentene-1), poly(3-methylbutene-1), poly(4-methylpentene-1), various ethylene-propylene copolymers and the like.
Other substrates in which the compounds of this invention are particularly useful are polystyrene, including impact polystyrene, ABS resin, SBR, isoprene, as well as natural rubber, polyesters including polyethylene terephthalate and polybutylene terephthalate, including copolymers. Also stabilized are polyurethanes, polycarbonates, polyamides such as nylon 6, 6/6 and the like as well as copolyamides and polysulfones.
The compounds of this invention may be used alone as the sole stabilizer having either mainly an antioxidant function or a light stabilizing function or the stabilizer may combine utility as an antioxidant and light stabilizer. The stabilizers may be used with phenolic antioxidants, lubricants such as calcium stearate, pigments, colorants or dyes, UV absorbers, light stabilizers such as hindered amines, metal deactivators, talc and other fillers, etc.
In general, the stabilizers of this invention are employed from about 0.01 to about 5% by weight of the stabilized composition, although this will vary with the particular substrate and application. An advantageous range is from about 0.05 to about 2%, and especially 0.1 to about 1%.
Compounds of this invention stabilize polymers especially during high temperature processing with relatively little change in color, even though the polymer may undergo a number of extrusions. Among the polymers in which this property is especially apparent are polypropylene, polyethylene, styrenics such as ABS, polyethylene- and polybutylene-terephthalates, polycarbonates, natural rubber, synthetic rubber such as SBR. While many compounds which have been used as process stabilizers are sufficiently effective as process stabilizers for polyolefins only in the presence of costabilizers such as phenolic antioxidants, compounds of this invention are effective in the absence of phenolic antioxidants. Many of the compounds of this invention combine process stabilizing properties with the ability to confer light stability on the polymer. This is particularly important for polymer fibers where processing temperatures are among the highest and where stability to actinic light is a prime requirement. A particularly important property for stabilizers which are trivalent phosphorus esters is their non-hygroscopicity and resistance to hydrolysis in the presence of moisture in the atmosphere during ambient storage. Hygroscopicity frequently results in difficulty in incorporating the process stabilizer uniformly into the polymer causing stickiness and blockage during compounding, while hydrolysis of the phosphorus ester stabilizers during storage frequently results in compounds which are less effective.
The stabilizers of formula I may readily be incorporated into the organic polymers by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The stabilized polymer compositions of the invention may optionally also contain various conventional additives, such as the following:
1. Antioxidants
1.1 Simple 2.6-dialkylphenols, such as, for example, 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.
1.2 Derivatives of alkylated hydroquinones, such as, for example, 2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amylhydroquinone, 2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, tris-(3,5-di-tert.-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.
1.3. Hydroxylated thiodiphenyl ethers, such as, for example, 2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulphide.
1.4. Alkylidene-bisphenols, such as, for example, 2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol), 4,4'-methylene-bis-(6-tert.-butyl-2-methylphenol), 4,4'-methylene-bis-(2,6-di-tert.-butylphenol), 2,6-di-(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol], 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)-butane, 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-pentane and ethylene glycol bis-[3,3-bis-(3'-tert.-butyl-4'-hydroxyphenyl)-butyrate].
1.5 O-, N- and S-benzyl compounds, such as, for example, 3,5,3',5'-tetra-tert.-butyl-4,4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.
1.6 Hydroxybenzylated malonates, such as, for example, dioctadecyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)-malonate, dioctadecyl 2-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercapto-ethyl 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate and di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate.
1.7 Hydroxybenzyl-aromatic compounds, such as, for example, 1,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-di-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-phenol.
1.8 s-Triazine compounds, such as, for example, 2,4-bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyanilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-s-triazine and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl) isocyanurate.
1.9 Amides of β-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid, such as, for example, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine. N,N'-(bis-β-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyl)-hydrazine.
1.10 Esters of β-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2,2,2]octane.
1.11 Esters of β-(5-tert.-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
1.12 Esters of 3,5-di-tert.-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiglycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]-octane, especially the tetra-bis ester of pentaerythritol.
1.13 Benzylphosphonates, such as, for example, dimethyl 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, diethyl 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate, dioctadecyl 3,5-di-tert.-butyl-4-hydroxybenzyl-phosphonate and dioctadecyl 5-tert.-butyl-4-hydroxy-3-methylbenzyl-phosphonate.
The following may be mentioned as examples of further additives that can be used together with the stabilizer of this invention and the antioxidant:
1. Aminoaryl derivatives, e.g. phenyl-1-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.-butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- and dioctyliminodibenzyl, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline. Octylated diphenylamine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sect.octyl-p-phenylenediamine, N-phenyl-N'-sec.-octyl-p-phenylenediamine, N,N'-di-(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-dimethyl-N,N'-di-(sec.-octyl)-p-phenylenediamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.-butylaniline, diphenylamineacetone condensation product, aldol-1-naphthylamine and phenothiazine.
Discoloration effects have to be taken into account when using the above antioxidants.
2. UV-Absorbers and light-stabilising agents
2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, e.g. the 5'-methyl-, 3',5'-di-tert.-butyl-, 5'-tert.-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.-butyl-, 5-chloro-3'-tert.-butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl-, 3'-α-methylbenzyl-5'-methyl-, 3'-α-methylbenzyl-5'-methyl-5-chloro-, 4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-amyl-, 3'-methyl-5'-carbomethoxyethyl- and 5-chloro-3',5'-di-tert.-amyl-derivative.
2.2. 2,4-bis-(2'-Hydroxyphenyl)-6-alkyl-s-triazines, e.g. the 6-ethyl-, 6-heptadecyl- or 6-undecyl-derivative.
2.3. 2-Hydroxybenzophenones, e.g. the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy-derivative.
2.4. 1,3-bis-(2'-Hydroxybenzoyl)-benzenes, e.g. 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene or 1,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.
2.5. Esters of optionally substituted benzoic acids, e.g. phenylsalicylate, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoylresorcin, 3,5-di-tert.-butyl-4-hydroxybenzoic acid-2,4-di-tert.-butylphenyl ester or -octadecyl ester or -2-methyl-4,6-di-tert.-butyl ester.
2.6. Acrylates, e.g. α-cyano-β,β-diphenylacrylic acid-ethyl ester or -isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester or N-(β-carbomethoxyvinyl)-2-methyl-indoline.
2.7. Sterically hindered amines, e.g. 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-tetramethylpiperidyl)-sebacate or 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4,5]decane-2,4-dione.
2.8. Oxalic acid diamides, e.g. 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.-butyl-oxanolide, 2,2'-di-dodecyloxy-5,5'-di-tert.-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide and the mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert.-butyl-oxanilide, or mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.
3. Metal deactivators, e.g. oxanilide, isophthalic acid dihyrazide, sebacic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetal-adipic acid dihydrazide, N,N'-bis-salicyloyloxalic acid dihydrazide, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenylpropionyl)hydrazine, N-salicyloyl-N'-salicylalhydrazine, 3-salicyloylamino-1,2,4-triazole or N,N'-bis-salicyloyl-thiopropionic acid dihydrazide.
4. Basic co-stabilisers, e.g. alkali metal salts and alkaline-earth metal salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-behenate, Na-ricinoleate or K-palmitate.
5. Nucleation agents, e.g. 4-tert.-butylbenzoic acid, adipic acid or diphenylacetic acid.
6. Phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphospha[5,5]-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.
Other additives that can be incorporated in the stabilized compositions are thiosynergists such as dilaurylthiodiproprionate or distearylthiodipropionate, lubricants such as stearyl alcohol fillers, carbon black, asbestos, kaolin, talc, glass fibers, pigments, optical brighteners, flameproofing agents and antistatic agents.
EXAMPLE 1 Preparation of (3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphorochloride
45.21 grams of phosphorus trichloride in 50 ml of toluene was added dropwise over 85 minutes to a solution of 123.0 grams of 3,3',5,5'-tetra-tert.-butyl-2,2'-dihydroxy-1,1'-biphenyl and 60.6 grams of triethylamime in about 600 ml of toluene and stirred at room temperature overnight (about 20 hours). The reaction product was filtered free of triethylamine hydrochloride, the desired product being isolated by removal of the solvent at reduced pressure to yield a solid m.p. 168°-174°.
______________________________________                                    
       Analysis       % C1                                                
______________________________________                                    
       Calcd.         7.46                                                
       Found          7.50                                                
______________________________________
EXAMPLE 2 O-(2,4-di-tert.-butylphenyl)-O1, O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite
4.85 grams of 46.3% aqueous potassium hydroxide was added to a solution of 8.24 grams of 2,4-di-tert.-butylphenol in 250 ml of toluene and heated at reflux over a period of about 2 hours until all the water including reaction water was removed by azeotropic distillation yielding a dispersion of the potassium 2,4-di-tert.-butylphenolate in toluene. To this dispersion at -5° was added a solution of 21.7 grams of the compound of Example 1 in 60 ml of toluene at -5° to -3° over a period of 25 minutes and then stirring continued overnight. The reaction mixture was clarified by filtration of the precipitated potassium chloride and the product isolated as a residue by distillation of the toluene at reduced pressures. The product was isolated as crystals after crystallization from a solvent mixture of acetonitrile and toluene yielding white crystals melting at 195°-197°.
______________________________________                                    
Analysis:       % C          % H                                          
______________________________________                                    
Calcd.          78.22        9.53                                         
Found           78.56        9.86                                         
______________________________________
EXAMPLE 3 O-2,6-di-tert.-butyl-4-methylpenyl)-O1,O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite
The compound of this example was made by substantially the same method as Example 2 by reacting (4,4'-6,6'-tetra-tert.-butyl-2,2'-biphenylene)phosphorochlorodite with potassium 2,6-di-tert.-butyl-4-methylphenolate. After crystallization, the product is obtained as white crystals melting at 152°-155° C.
EXAMPLE 4 O-(2,4,6-tri-tert.-butylphenyl)-O1,O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite
The compound of this example was made by substantially the same method as Example 2 by reacting 3,3',5,5'-tetra-tert.butyl-1,1'-biphenyl-2,2'-diyl) phosphorochlorodite with potassium 2,4,6-tri-tert. phenolate. After crystallization, the product is obtained as white crystals melting at 210°-212°.
EXAMPLE 5 O-iso-propyl-O1,O2,-(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)
A solution of 23.75 grams of the chloridite of Example 1 in 80 ml of toluene was added dropwise at 15°-20° C. to 3.0 grams of isopropanol dissolved in 50.5 grams of triethylamine and stirring continued overnight at room temperature. After being filtered free of triethylamine hydrochloride and removal of volatiles at reduced pressures, the resulting residue was crystallized from isopropanol yielding the product as white crystals melting at 154°-156° C.
______________________________________                                    
Analysis:       % C          % H                                          
______________________________________                                    
Calcd.          74.66        9.42                                         
Found           74.34        9.73                                         
______________________________________
EXAMPLE 6 S,S'(trimethylene)bis-(O,O1 (3,3'5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)thiophosphite)
The compound of this Example was made by the same procedure as Examples by reacting two molar proportions of tetra-3,3'5,5'-tert.butyl -1,1'-biphenyl-2,2'-diyl phosphorochloridite (Example 1) with one molar proportion of 1,3-propanedithiol in the presence to triethylamine. After crystallization the product melted at 190°-193° C.
EXAMPLE 7 O,O'(4,4'-methylene-bis-(2,6-di-tert-butylphenylene))-O1,O2))3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-1,1'-diyl)phosphite)
The compound of this example is made by the same procedure as Example 5 by reacting two molar proportions of the chloridite of Example IV with one molar proportion of 4,4'-methylene-bis (2,6-di-tert.-butylphenol) in the presence of triethylamine.
EXAMPLE 8 O- n-octadecyl-O1,O2 -(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl2,2'-diyl) phosphite
The compound of this example was made by substantially the same procedure as Example 5 by reacting equimolar quantities of the chloridite of Example 1 with n-octadecanol in the presence of triethylamine. After purification by chromatography and by crystallization the product was obtained as white crystals melting at 38°-41° C.
Following the procedure of Example 5, the following compounds are prepared by reacting the appropriate starting materials.
__________________________________________________________________________
 ##STR3##                                                                 
Ex. No.                                                                   
     R     R.sup.1 X R.sup.2                                              
__________________________________________________________________________
 9   (CH.sub.3).sub.3 C                                                   
           4(CH.sub.3).sub.3 C                                            
                   OCH.sub.3                                              
                   (mp 190°-192° C.)                        
10   C.sub.8 H.sub.18                                                     
           4CH.sub.3                                                      
                   OC.sub.18 H.sub.38                                     
11*  (CH.sub.3).sub.3 C                                                   
           4(CH.sub.3).sub.3 C                                            
                    ##STR4##                                              
                   (mp 255°-258° C.)                        
12   (CH.sub.3).sub.3 C                                                   
           5CH.sub.3                                                      
                   OC.sub.8 H.sub.18                                      
13   (CH.sub.3).sub.3 C                                                   
           4(CH.sub.3).sub.3 C                                            
                    ##STR5##                                              
14   (CH.sub.3).sub.3 C                                                   
           4(CH.sub.3).sub.3 C                                            
                    ##STR6##                                              
15** (CH.sub.3).sub.3 C                                                   
           4(CH.sub.3).sub.3 C                                            
                   OCH.sub.2C(CH.sub.3).sub.2CH.sub.2 O                   
                   (mp 165°-168° C.)                        
16   (CH.sub.3).sub.3 C                                                   
           r(CH.sub.3).sub.3 C                                            
                   SC.sub.8 H.sub.17                                      
__________________________________________________________________________
 *The alcohol used was methanol with the chloridate:alcohol ratio of 1:1  
 **The alcohol used was 2,2dimethyl-1-1.3 propanediol with the            
 chloridite:alcohol ratio of 2:1.
EXAMPLE 17 Processing Stability of Polypropylene at 500° F. 
______________________________________                                    
Base Formulation:                                                         
______________________________________                                    
Profax 6801            100 parts                                          
Calcium stearate       0.10 parts                                         
______________________________________
Stabilizers were solvent blended into polypropylene as solutions in methylene chloride and, after removal of the solvent by evaporation at reduced pressure, the resin was extruded using the following extruder conditions:
______________________________________                                    
               Temp.                                                      
               °F.       (°C.)                              
______________________________________                                    
Cylinder #1  --      450              232                                 
Cylinder #2  --      475              246                                 
Cylinder #3  --      500              260                                 
Die #1       --      500              260                                 
Die #2       --      500              260                                 
RPM          --                100                                        
______________________________________
During extrusion, the internal extruder pressure was determined using a pressure transducer. After each of the first, third and fifth extrusions, resin pellets were compression molded into 125 mil (3.2 mm) thick plaques at 380° F. (193° F.) and specimen yellowness index (Y.I.) determined according to ASTM D1925-63T.
The melt flow rate (MFR) was determined by ASTM method 1238 condition L. The melt flow rate varies directly as the transducer pressure and both are a measure of the molecular weight for a specific type of polymer.
The data is presented in Table I below.
                                  Table 1                                 
__________________________________________________________________________
         (psi)    **       YI Color***                                    
         Transducer Pres-                                                 
                  MFR (g/10min)                                           
                           after                                          
         sure After Ext.                                                  
                  After Ext.                                              
                           Extrusion                                      
Additive 1  3  5  1  3  5  1  3  5                                        
__________________________________________________________________________
None     1095                                                             
            840                                                           
               655                                                        
                  0.73                                                    
                     2.01                                                 
                        4.25                                              
                           4.6                                            
                              6.5                                         
                                 7.9                                      
0.1 Antiox. A*                                                            
         1215                                                             
            1045                                                          
               930                                                        
                  0.42                                                    
                     1.04                                                 
                        1.25                                              
                           6.7                                            
                              8.6                                         
                                 10.5                                     
0.15 Antiox. A*                                                           
         1270                                                             
            1110                                                          
               990                                                        
                  0.40                                                    
                     0.78                                                 
                        1.06                                              
                           7.8                                            
                              10.3                                        
                                 12.5                                     
The following contain 0.1% Antioxidant A and a compound as                
indicated below:                                                          
0.05 Cmpd.Ex.2                                                            
         1260                                                             
            1125                                                          
               1035        5.9                                            
                              7.4                                         
                                 9.9                                      
0.05 Cmpd.Ex.3                                                            
         1250                                                             
            1080                                                          
               1020        5.9                                            
                              8.0                                         
                                 9.3                                      
0.05 Cmpd.Ex.4                                                            
         1230                                                             
            1120                                                          
               1010        6.1                                            
                              8.6                                         
                                 10.3                                     
0.05 Cmpd.Ex.5                                                            
         1380                                                             
            1275                                                          
               1200        4.8                                            
                              6.1                                         
                                 7.8                                      
0.05 Cmpd.Ex.8                                                            
         1350                                                             
            1260                                                          
               1170        5.3                                            
                              7.1                                         
                                 9.0                                      
0.05 Cmpd.Ex.9                                                            
         1335                                                             
            1260                                                          
               1200                                                       
                  0.19                                                    
                     0.24                                                 
                        0.36                                              
                           5.4                                            
                              6.6                                         
                                 8.5                                      
0.05 Cmpd.Ex.6                                                            
         1335                                                             
            1260                                                          
               1230                                                       
                  0.19                                                    
                     0.25                                                 
                        0.34                                              
                           5.9                                            
                              6.7                                         
                                 8.2                                      
0.05 Cmpd.Ex.15                                                           
         1375                                                             
            1275                                                          
               1230                                                       
                  0.20                                                    
                     0.24                                                 
                        0.31                                              
                           5.7                                            
                              7.1                                         
                                 8.1                                      
0.05 Cmpd.Ex.11                                                           
         1245                                                             
            1155                                                          
               1080                                                       
                  0.27                                                    
                     0.38                                                 
                        0.56                                              
                           5.9                                            
                              7.4                                         
                                 8.5                                      
__________________________________________________________________________
 *Antioxidant A is pentaerithritol tetrakis [3-(3',5'-di-tert.            
 butyl4-'-hydroxyphenyl) propionate]-                                     
 **Melt flow rate                                                         
 ***Yellowness Index

Claims (23)

What is claimed is:
1. A 1,1'-biphenylene phosphite of the formula ##STR7## wherein R is an alkyl group of 1 to 18 carbon atoms,
R1 is hydrogen or an alkyl group of 1 to 18 carbon atoms and
R2 is an alkyl group of 1 to 18 carbon atoms, phenyl, phenyl substituted with up to 3 alkyl groups each having 1 to 8 carbon atoms, or a group of the formula ##STR8## where R3 is a divalent hydrocarbyl group selected from alkylene, arylene or allylene, and X is oxygen or sulfur.
2. A compound of claim 1 wherein
R is an α-branched alkyl radical of 3 to 8 carbon atoms,
R1 is an alkyl of 1 to 8 carbon atoms
R2 is a phenyl group having at least one branched alkyl group or a 1,1'-biphenylene phosphite group.
3. A compound of claim 2 wherein
R1 is in the meta position to the R group.
4. A compound of claim 3 wherein
R is tert-butyl or tert-octyl,
R1 is a tert-alkyl group of 4 to 8 carbon atoms,
R2 is selected from the group consisting of 2-tert-butylphenyl, 2,4-di-tert-butyl-phenyl, 2,4,6-tri-tert-butylphenyl, 2-tert-butyl-5-methylphenyl, 2,6-di-tert-butyl-phenyl and 2,6-di-tert-butyl-4-methyl-phenyl, 2,4-di-tert-octylphenyl.
5. A compound of claim 4 wherein
R2 is a group of the formula ##STR9## where X is oxygen and
R3 is an alkylene of 1 to 12 carbon atoms or arylene.
6. The compound of claim 1 which is O-(2,4-di-tert.-butylphenyl-O1, O2 -3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2-diyl)phosphite.
7. The compound of claim 1 which is O-(2,6-di-tert.-butyl-4-methylphenyl)-O1,O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite.
8. The compound of claim 1 which is O-(2,2,6-tri-tert.-butylphenyl)O1,O2 -3,3'5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite.
9. The compound of claim 1 which is O-Isopropyl-O1,O2 -(3,3',5,5',-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite.
10. The compound of claim 1 which is S,S'(Trimethylene)bis-(O,O'-(3,3',5,5'-tetra-tert.-butyl-1,1'biphenyl2,2'-diyl)thiophosphite).
11. The compound of claim 1 which is O,O'(4,4'-methylene-bis-(2,6-di-tert.-butylphenylene)-O1,O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite).
12. The compound of claim 1 which is O-(n-octadecyl-O1,O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl2,2'-diyl)phosphite.
13. The compound of claim 1 which is O-methyl-O1,O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite.
14. The compound of claim 1 which is O,O'(2,2-dimethylpropylene)-O1,O2 -bis(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphite.
15. A composition of matter comprising an organic material subject to oxidative, thermal and actinic degradation stabilized with a compound of claim 1.
16. A composition of matter of claim 15 wherein the organic material is a synthetic polymer.
17. A composition of claim 16 wherein the polymer is a polyolefin homopolymer or copolymer.
18. A polyolefin homopolymer or copolymer stabilized with the compound of claim 10.
19. A composition of claim 17 stabilized with the compound of claim 13.
20. A composition of claim 17 stabilized with the compound of claim 14.
21. A composition of claim 17 stabilized with the compound of claim 9.
22. The compound of claim 1 which is O-ethyl-O1,O2 -(3,3'5,5'-tetramethyl-1-1'-biphenyl-2,2'-diyl)phosphite.
23. The compound of claim 1 which is O-ethyl-O1,O2 -(3,3',5,5'-tetra-tert.-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.
US05/866,748 1978-01-03 1978-01-03 Alkylated 1,1'-biphenyl-2,2'-diyl phosphites and stabilized compositions Expired - Lifetime US4196117A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US05/866,748 US4196117A (en) 1978-01-03 1978-01-03 Alkylated 1,1'-biphenyl-2,2'-diyl phosphites and stabilized compositions
EP78101825A EP0002821B1 (en) 1978-01-03 1978-12-22 Cyclic phosphites and organic material stabilized by them
DE7878101825T DE2861920D1 (en) 1978-01-03 1978-12-22 Cyclic phosphites and organic material stabilized by them
JP16457378A JPS54100391A (en) 1978-01-03 1978-12-29 Alkylated 2*2**biphenylphosphite and stabilized composition
CA318,804A CA1104580A (en) 1978-01-03 1978-12-29 Alkylated 2,2'-biphenylene phosphites and stabilized compositions
US06/093,786 US4288391A (en) 1978-01-03 1979-11-13 Alkylated 2,2'-biphenylene phosphites
US06/246,341 US4351759A (en) 1978-01-03 1981-03-23 Alkylated 2,2'-biphenylene phosphites and stabilized compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/866,748 US4196117A (en) 1978-01-03 1978-01-03 Alkylated 1,1'-biphenyl-2,2'-diyl phosphites and stabilized compositions

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US06/093,786 Continuation-In-Part US4288391A (en) 1978-01-03 1979-11-13 Alkylated 2,2'-biphenylene phosphites

Publications (1)

Publication Number Publication Date
US4196117A true US4196117A (en) 1980-04-01

Family

ID=25348324

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/866,748 Expired - Lifetime US4196117A (en) 1978-01-03 1978-01-03 Alkylated 1,1'-biphenyl-2,2'-diyl phosphites and stabilized compositions

Country Status (5)

Country Link
US (1) US4196117A (en)
EP (1) EP0002821B1 (en)
JP (1) JPS54100391A (en)
CA (1) CA1104580A (en)
DE (1) DE2861920D1 (en)

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4288391A (en) * 1978-01-03 1981-09-08 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphites
US4308193A (en) * 1978-04-26 1981-12-29 Olin Corporation Halogenated tertiary phosphite esters
US4321218A (en) * 1978-01-10 1982-03-23 Ciba-Geigy Corporation Phosphite stabilizer
US4348495A (en) * 1978-08-24 1982-09-07 Bayer Aktiengesellschaft Phosphorous acid esters and their use for stabilizing polyamides
US4351759A (en) * 1978-01-03 1982-09-28 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphites and stabilized compositions
US4362830A (en) * 1980-01-10 1982-12-07 Adeka Argus Chemical Co., Ltd. Hindered bis-phenol phenyl phosphites and synthetic resin compositions having enhanced stability to heat and light
US4371646A (en) * 1979-12-26 1983-02-01 Adeka Argus Chemical Co. Ltd. 2,6-Di-tertiary butyl phenyl phosphites and synthetic resin compositions having enhanced stability to heat and light
US4405739A (en) * 1981-11-17 1983-09-20 General Electric Company Polyphenylene ether resins and compositions heat stabilized with phosphite compounds
US4414345A (en) * 1978-05-18 1983-11-08 Ciba-Geigy Corporation Compositions stabilized with dioxaphosphepines
US4416829A (en) * 1982-10-06 1983-11-22 Standard Oil Company (Indiana) Poly-hindered phenol-phosphites and process for preparation
US4433087A (en) * 1978-01-03 1984-02-21 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphonates and stabilized compositions
US4483953A (en) * 1981-10-28 1984-11-20 General Electric Company Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphite
US4524166A (en) * 1982-11-01 1985-06-18 Ciba-Geigy Corporation Primary or secondary amino substituted dibenzo dioxaphosphepins and dioxaphosphocins
US4599206A (en) * 1984-02-17 1986-07-08 Union Carbide Corporation Transition metal complex catalyzed reactions
US4668651A (en) * 1985-09-05 1987-05-26 Union Carbide Corporation Transition metal complex catalyzed processes
US4717775A (en) * 1984-12-28 1988-01-05 Union Carbide Corporation Transition metal complex catalyzed reactions
US4748261A (en) * 1985-09-05 1988-05-31 Union Carbide Corporation Bis-phosphite compounds
US4808645A (en) * 1985-04-29 1989-02-28 Ciba-Geigy Corporation 6-(1-hydro-2,2,6,6-tetraalkyl-piperidine-4-oxy)dibenzodioxaphosphepin and dioxaphosphocin process stabilizers
US4867907A (en) * 1987-07-27 1989-09-19 Ethyl Corporation Aqueous aryl fluorophosphite suspension
US4885401A (en) * 1985-09-05 1989-12-05 Union Carbide Corporation Bis-phosphite compounds
US5039723A (en) * 1988-09-16 1991-08-13 Adeka Argus Chemical Co., Ltd. Stabilized synthetic resin composition
US5292785A (en) * 1992-05-05 1994-03-08 Ciba-Geigy Corporation Bis-phosphite stabilized compositions
US5310889A (en) * 1992-07-22 1994-05-10 Ciba-Geigy Corporation Carbohydrate substituted dibenzo(d,f)(1,3,2)dioxaphosphepin stabilizers
US5310890A (en) * 1992-07-22 1994-05-10 Ciba-Geigy Corporation Carbohydrate substituted dibenzoi(d,g)(1,3,2)dioxaphosphocin stabilizers
US5424348A (en) * 1993-07-22 1995-06-13 General Electric Company Neo-diol phosphites as polymer stabilizers
US5500467A (en) * 1993-07-22 1996-03-19 General Electric Company Polyolefin fiber and film resistant to gas fade
US5500468A (en) * 1993-07-22 1996-03-19 General Electric Company Process for stabilizing polymeric material
US5543102A (en) * 1993-07-22 1996-08-06 General Electric Company Melt extrusion process
US5559167A (en) * 1993-07-22 1996-09-24 General Electric Company Gamma irradiated thermoplastics and articles
US5594053A (en) * 1996-01-22 1997-01-14 General Electric Company Aromatic cyclic bisphosphite esters and polymeric compositions thereof
US5605947A (en) * 1993-07-22 1997-02-25 General Electric Company Amorphous neo-diol phosphite compositions
US5614571A (en) * 1994-09-16 1997-03-25 General Electric Company Stabilizer blend containing phosphite
US5618866A (en) * 1996-01-22 1997-04-08 General Electric Company Neo diol phosphite esters and polymeric compositions thereof
US5786497A (en) * 1997-08-29 1998-07-28 General Electric Company Process for the preparation of phosphites
US5917076A (en) * 1998-04-16 1999-06-29 General Electric Company Process for the preparation of spiro bis-phosphites using finely ground pentaerythritol
US5919966A (en) * 1998-03-26 1999-07-06 General Electric Company Process for the preparation of spiro bis-phosphites
US20070108417A1 (en) * 2005-11-16 2007-05-17 Kenji Kimura Antioxidant composition excellent in anti-blocking property
US20090326115A1 (en) * 2008-06-26 2009-12-31 Sumitomo Chemical Company, Limited Polyester compositions

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2087399B (en) * 1980-11-17 1983-11-02 Ciba Geigy Ag Polyol esters of alkylidine-2,2' -bisphenyl cyclic phosphites
US4318845A (en) * 1980-11-24 1982-03-09 Ciba-Geigy Corporation Alkanolamine esters of 1,1'-biphenyl-2,2'-diyl-and alkylidene-1,1'-biphenyl-2,2'-diyl-cyclic phosphites
EP0108714A1 (en) * 1982-10-13 1984-05-16 Ciba-Geigy Ag Dibenzodioxaphosphepine and dioxaphosphocine processing stabilizers
US4605692A (en) * 1984-12-17 1986-08-12 Ciba-Geigy Corporation Substituted dibenzo dioxaphosphepins and dioxaphosphocins as stabilizers
JPS63105053A (en) * 1986-10-20 1988-05-10 Kuraray Co Ltd Polyester resin having excellent light resistance
GB8625149D0 (en) * 1986-10-21 1986-11-26 Kodak Ltd Stabilisation of dye images
DE3706044A1 (en) * 1987-02-25 1988-09-08 Bayer Ag STABILIZED MIXTURES OF THERMOPLASTIC POLYESTER AND RUBBER-ELASTIC POLYMERISAT, METHOD FOR THE PRODUCTION OF THESE MIXTURES AND THE USE THEREOF FOR THE PRODUCTION OF MOLDED BODIES
GB8808694D0 (en) * 1988-04-13 1988-05-18 Kodak Ltd Stabilization of dye images produced in photographic materials
JP3369743B2 (en) * 1994-07-22 2003-01-20 旭電化工業株式会社 Synthetic resin composition
DE4431528A1 (en) * 1994-09-03 1996-03-07 Basf Ag Process for the preparation of n-butyraldehyde and / or n-butanol
DE19607459C1 (en) * 1996-02-28 1997-07-24 Bayer Ag Process for the preparation of trialkyl phosphites
JP6170059B2 (en) * 2011-10-31 2017-07-26 ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー Prevention of crystallization solvents in the production of polyphosphite ligands

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297631A (en) * 1965-10-24 1967-01-10 Exxon Research Engineering Co Novel phenolic phosphorus stabilizers for polyolefins
US3415906A (en) * 1964-05-29 1968-12-10 Hooker Chemical Corp Phosphite phospholane and phosphorinane compounds
US3558554A (en) * 1966-06-09 1971-01-26 Yoshitomi Pharmaceutical Oxidatively stable polyolefin composition
US3796684A (en) * 1967-08-31 1974-03-12 Borg Warner Polymer compositions stabilized with substituted 4,5-benzo-1,3,2-dioxaphospholanes
US4094855A (en) * 1976-07-30 1978-06-13 Ciba-Geigy Corporation Hindered phenyl phosphites

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU274293A (en) *
FR1481912A (en) * 1962-11-28 1967-05-26 Argus Chem Organic phosphites and synthetic resin compositions containing phosphites
SU378389A1 (en) * 1971-02-08 1973-04-18 Method of producing styrene-copolymers iacrylonitrile
SU429070A1 (en) * 1971-06-06 1974-05-25 METHOD FOR OBTAINING A COLORLESS COPOLYMER. TESTER WITH ACRYLONITRILE 1 The invention relates to the production of polystyrene plastics, in particular, to the preparation of styrene and acrylonitrile copolymers that are resistant to color change under the conditions of processing into products. slightly yellowish materials. Heating them briefly at 50–180 ° C, especially at 200–220 ° C, associated with the processing of the material, leads to a change in color. The copolymer becomes much yellower and even darker. A method is known for preparing color-resistant copolymers by thermal polymerization in an inert gas atmosphere of 80–60 wt. % styrene and 20-40 weight. % acrylonitrile in the presence of 0.05 ^ 0.25 wt. % organophosphorus compound of general formula 1015 where RI is alkyl (Ci — € 4); Ro is alkyl (Ci — Sat); Rs is alkyl (Ci — GS), aryl or alkaryl. This method makes it possible to obtain copolymers that are resistant to color change at a processing temperature of 200–220 ° C for 30–40 minutes. The purpose of the invention is to obtain copolymers that are resistant to temperatures of 200–220 ° C for a long time. . This is achieved by copolymerization in an inert gas atmosphere at elevated temperatures of 80–60 wt. % styrene with 20-40 weight. % acrylonitrile in the presence of a mixture consisting of 0.05-0.25 weight. % 2,4,6-trialkylphenol of the general formula 2025CCH ^) ^ CCICH ^) ^ where R is alkyl (Ci — 4), and an organophosphorus compound with a total of 30 formulas

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415906A (en) * 1964-05-29 1968-12-10 Hooker Chemical Corp Phosphite phospholane and phosphorinane compounds
US3297631A (en) * 1965-10-24 1967-01-10 Exxon Research Engineering Co Novel phenolic phosphorus stabilizers for polyolefins
US3558554A (en) * 1966-06-09 1971-01-26 Yoshitomi Pharmaceutical Oxidatively stable polyolefin composition
US3796684A (en) * 1967-08-31 1974-03-12 Borg Warner Polymer compositions stabilized with substituted 4,5-benzo-1,3,2-dioxaphospholanes
US4094855A (en) * 1976-07-30 1978-06-13 Ciba-Geigy Corporation Hindered phenyl phosphites

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kirpichnikov et al., Chem. Abs., vol. 73, 1970, 15657a. *

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4433087A (en) * 1978-01-03 1984-02-21 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphonates and stabilized compositions
US4288391A (en) * 1978-01-03 1981-09-08 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphites
US4351759A (en) * 1978-01-03 1982-09-28 Ciba-Geigy Corporation Alkylated 2,2'-biphenylene phosphites and stabilized compositions
US4321218A (en) * 1978-01-10 1982-03-23 Ciba-Geigy Corporation Phosphite stabilizer
US4308193A (en) * 1978-04-26 1981-12-29 Olin Corporation Halogenated tertiary phosphite esters
US4414345A (en) * 1978-05-18 1983-11-08 Ciba-Geigy Corporation Compositions stabilized with dioxaphosphepines
US4348495A (en) * 1978-08-24 1982-09-07 Bayer Aktiengesellschaft Phosphorous acid esters and their use for stabilizing polyamides
US4371646A (en) * 1979-12-26 1983-02-01 Adeka Argus Chemical Co. Ltd. 2,6-Di-tertiary butyl phenyl phosphites and synthetic resin compositions having enhanced stability to heat and light
US4362830A (en) * 1980-01-10 1982-12-07 Adeka Argus Chemical Co., Ltd. Hindered bis-phenol phenyl phosphites and synthetic resin compositions having enhanced stability to heat and light
US4483953A (en) * 1981-10-28 1984-11-20 General Electric Company Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphite
US4405739A (en) * 1981-11-17 1983-09-20 General Electric Company Polyphenylene ether resins and compositions heat stabilized with phosphite compounds
US4416829A (en) * 1982-10-06 1983-11-22 Standard Oil Company (Indiana) Poly-hindered phenol-phosphites and process for preparation
US4524166A (en) * 1982-11-01 1985-06-18 Ciba-Geigy Corporation Primary or secondary amino substituted dibenzo dioxaphosphepins and dioxaphosphocins
US4599206A (en) * 1984-02-17 1986-07-08 Union Carbide Corporation Transition metal complex catalyzed reactions
US4717775A (en) * 1984-12-28 1988-01-05 Union Carbide Corporation Transition metal complex catalyzed reactions
US4808645A (en) * 1985-04-29 1989-02-28 Ciba-Geigy Corporation 6-(1-hydro-2,2,6,6-tetraalkyl-piperidine-4-oxy)dibenzodioxaphosphepin and dioxaphosphocin process stabilizers
US4885401A (en) * 1985-09-05 1989-12-05 Union Carbide Corporation Bis-phosphite compounds
US4769498A (en) * 1985-09-05 1988-09-06 Union Carbide Corporation Transition metal complex catalyzed processes
US4748261A (en) * 1985-09-05 1988-05-31 Union Carbide Corporation Bis-phosphite compounds
US4668651A (en) * 1985-09-05 1987-05-26 Union Carbide Corporation Transition metal complex catalyzed processes
US4867907A (en) * 1987-07-27 1989-09-19 Ethyl Corporation Aqueous aryl fluorophosphite suspension
US5039723A (en) * 1988-09-16 1991-08-13 Adeka Argus Chemical Co., Ltd. Stabilized synthetic resin composition
US5292785A (en) * 1992-05-05 1994-03-08 Ciba-Geigy Corporation Bis-phosphite stabilized compositions
US5310889A (en) * 1992-07-22 1994-05-10 Ciba-Geigy Corporation Carbohydrate substituted dibenzo(d,f)(1,3,2)dioxaphosphepin stabilizers
US5310890A (en) * 1992-07-22 1994-05-10 Ciba-Geigy Corporation Carbohydrate substituted dibenzoi(d,g)(1,3,2)dioxaphosphocin stabilizers
US5414028A (en) * 1992-07-22 1995-05-09 Ciba-Geigy Corporation Carbohydrate substituted dibenzo[d,f][1,3,2]dioxaphosphepin stabilizers
US5543102A (en) * 1993-07-22 1996-08-06 General Electric Company Melt extrusion process
US5623009A (en) * 1993-07-22 1997-04-22 General Electric Company Neo-diol phosphites as polymer stabilizers
US5500468A (en) * 1993-07-22 1996-03-19 General Electric Company Process for stabilizing polymeric material
US5424348A (en) * 1993-07-22 1995-06-13 General Electric Company Neo-diol phosphites as polymer stabilizers
US5559167A (en) * 1993-07-22 1996-09-24 General Electric Company Gamma irradiated thermoplastics and articles
US5500467A (en) * 1993-07-22 1996-03-19 General Electric Company Polyolefin fiber and film resistant to gas fade
US5605947A (en) * 1993-07-22 1997-02-25 General Electric Company Amorphous neo-diol phosphite compositions
US5614571A (en) * 1994-09-16 1997-03-25 General Electric Company Stabilizer blend containing phosphite
US5594053A (en) * 1996-01-22 1997-01-14 General Electric Company Aromatic cyclic bisphosphite esters and polymeric compositions thereof
US5618866A (en) * 1996-01-22 1997-04-08 General Electric Company Neo diol phosphite esters and polymeric compositions thereof
US5786497A (en) * 1997-08-29 1998-07-28 General Electric Company Process for the preparation of phosphites
US5919966A (en) * 1998-03-26 1999-07-06 General Electric Company Process for the preparation of spiro bis-phosphites
US5917076A (en) * 1998-04-16 1999-06-29 General Electric Company Process for the preparation of spiro bis-phosphites using finely ground pentaerythritol
US20070108417A1 (en) * 2005-11-16 2007-05-17 Kenji Kimura Antioxidant composition excellent in anti-blocking property
US7883642B2 (en) * 2005-11-16 2011-02-08 Sumitomo Chemical Company, Limited Antioxidant composition excellent in anti-blocking property
US20090326115A1 (en) * 2008-06-26 2009-12-31 Sumitomo Chemical Company, Limited Polyester compositions
US7994247B2 (en) * 2008-06-26 2011-08-09 Sumitomo Chemical Company, Limited Polyester compositions

Also Published As

Publication number Publication date
JPS54100391A (en) 1979-08-08
DE2861920D1 (en) 1982-08-12
EP0002821A1 (en) 1979-07-11
EP0002821B1 (en) 1982-06-23
CA1104580A (en) 1981-07-07
JPS6245875B2 (en) 1987-09-29

Similar Documents

Publication Publication Date Title
US4196117A (en) Alkylated 1,1'-biphenyl-2,2'-diyl phosphites and stabilized compositions
US4374219A (en) Alkanolamine ester of 1,1-biphenyl-2,2-diyl-and alkylidene-1,1-biphenyl-2,2-diyl-cyclic phosphites
US4318845A (en) Alkanolamine esters of 1,1'-biphenyl-2,2'-diyl-and alkylidene-1,1'-biphenyl-2,2'-diyl-cyclic phosphites
US4351759A (en) Alkylated 2,2'-biphenylene phosphites and stabilized compositions
US4094855A (en) Hindered phenyl phosphites
US4143028A (en) Alkylated 1,1'-biphenyl-2,2'-diyl phosphonites and stabilized compositions
US4180498A (en) Hindered phenyl phosphites
JPH0463871B2 (en)
US4474914A (en) Ortho-alkylated phenyl phosphonites and stabilized organic compositions
CA1159845A (en) Polyol esters of alkylidene-2,2'-bis-phenyl cyclic phosphites
US4288391A (en) Alkylated 2,2'-biphenylene phosphites
US4406842A (en) Ortho-alkylated phenyl phosphonites
US4207229A (en) Hindered phenyl phosphites
US4233207A (en) Hydrolytically stable ortho-alkylated phenyl phosphonites and stabilized compositions
US4433087A (en) Alkylated 2,2'-biphenylene phosphonates and stabilized compositions
US4808645A (en) 6-(1-hydro-2,2,6,6-tetraalkyl-piperidine-4-oxy)dibenzodioxaphosphepin and dioxaphosphocin process stabilizers
WO2001032765A1 (en) Non-xenoestrogenic phosphite stabilizers for organic materials
US5773498A (en) Diphosphites
US4524166A (en) Primary or secondary amino substituted dibenzo dioxaphosphepins and dioxaphosphocins
US4182704A (en) Hindered phenyl phosphites
US4456716A (en) 4-(Hydroxyphenylthio)imide stabilizers
US4503243A (en) Dioxasilepin and dioxasilocin stabilizers
CA1117546A (en) Hydrolytically stable ortho-alkylated phenyl phosphonites and stabilized compositions
US4582870A (en) Dioxasilepin and dioxasilocin stabilizers
US4524167A (en) Polymeric hindered phosphonate stabilizers

Legal Events

Date Code Title Description
AS Assignment

Owner name: CIBA SPECIALTY CHEMICALS CORPORATION, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CIBA-GEIGY CORPORATION;REEL/FRAME:008454/0057

Effective date: 19961227